WO2009151568A1 - Structured oil based systems - Google Patents

Abstract

A combination of an oligomer oil structurant, which includes urethane and/or urea linkages and residues of a dimer and/or trimer component, and a hydrogen bond disruptor, particularly a carboxylic acid; fatty amine; fatty carboxylic acid amide, alkylurea, or (poly)ether, particularly in a proportion of from 0.5 to 20 mol hydrogen bond disruptor per kg of oligomer oil structurant, can be incorporated into oils and activated to provide structure, particularly thickening and/or gelation, at temperatures well below the softening range of the oligomer and desirably at or near ambient temperature.

Description

STRUCTURED OIL BASED SYSTEMS

Cross Reference to Related Application

[0001] This application claims the benefit of priority from U.S. Provisional Application No.

61/129,197, filed June 10, 2008. This application, in its entirety, is incorporated herein by reference.

[0002] This invention relates to structurant systems for oil based formulations which use oligomeric urethane and/or urea linked structurants, particularly including dimer based units, and especially to modified systems including additives which generate fluid combinations with the structurant oligomers, while enabling ready formulation with oils to produce structured systems, and to oil based formulations structured using systems. [0003] PCT published application WO 2007/135384 A describes structured oil based agrochemical formulations based on oligomeric structurants including urethane and/or urea links, particularly using oligomers derived from dimer and/or trimer based feedstocks which can provide structured products what are clear (allowing for light scattering by any deliberately dispersed particularly solid materials), can suspend a high concentration of solids, retaining good stability at low addition levels and over a wide temperature range, with good tolerance for other components such as surfactants, dispersants, electrolytes and low molecular weight organic components such as alcohols. A potential disadvantage in using such oligomeric structurants is that the formulations need to be either made hot (or be heated) to properly activate the structurant on cooling. This is disadvantageous because it limits the use of the structurant to actives which are thermally stable - many pesticides e.g. sulphonyl ureas, are not thermally stable or are solublized at elevated temperatures; in practice it requires that the suspending oil has an adequately high flash point to permit safe incorporation of the structurant; and heating large quantities of oil is expensive. [0004] This invention is based on the discovery of a different approach to the formulation of dispersions, which uses additives which form combinations with the structurant oligomer that allow the incorporation of the structurant oligomer in oil based dispersion formulations at much reduced temperatures, desirably at ambient temperature, without a loss in the ability of the structurant oligomer to stabilise, and in particular to inhibit settling of particulates from, the dispersion formulation. The effect appears to relate to the ability of the additives to associate with and disrupt hydrogen bonding between polar segments of the molecules of the structurant oligomer allowing such polar segments of the oligomer to dissociate from each other. Subsequently when the oligomeric structurant is dispersed in the oil phase dilution and solvation by the oil enables such polar oligomer segments to link through hydrogen bonds thus enabling the structuring of the oil phase. [0005] The present invention accordingly provides a combination of an oligomer oil structurant which includes urethane and/or urea linkages and residues of a dimer and/or trimer component; and a hydrogen bond disruptor.

[0006] In particular the invention provides a structurant concentrate or masterbatch which comprises a structurant oligomer which includes urethane and/or urea linkages and residues of a dimer and/or trimer component; and a hydrogen bond disruptor in proportions from 0.5 to 20 moles hydrogen bond disruptor per kg oligomer.

[0007] The invention includes structured oil based formulation which comprises an oil; an oligomer oil structurant which includes urethane and/or urea linkages and residues of a dimer and/or trimer component; and a hydrogen bond disruptor. [0008] The invention is particularly applicable to the formulation of agrochemical concentrates and the invention accordingly includes an agrochemical concentrate which comprises an agrochemically active component dispersed in a structured oil system which comprises an oil and including as a structurant an oligomer including urethane and/or urea linkages and residues of a dimer and/or trimer component; and a hydrogen bond disruptor. [0009] The term "hydrogen bond disruptor" is used to mean a compound that interacts with hydrogen bonding systems involving the urethane or urea oligomer oil structurants, either as an electron donor or acceptor or proton donor or acceptor, more strongly than conventional solvents or diluents such as ketones like acetone and methyl ethyl ketone or plasticisers such as phthalates or phosphates. Suitable hydrogen bond disruptors are generally organic compounds which are co-soluble or miscible with the oligomeric oil structurant and include hydrogen bonding groups such as carboxyl, amine, amide, and ether especially polyether groups. We have found that moderately weak acids such as carboxylic, particularly alkanoic, acids; moderately weak bases such as medium to long chain alkyl amines; carboxylic acid amides; ethers, particularly ethers including adjacent aryl groups or, and especially, polyethers, particularly polyalkylene glycols and polyalkoxylates of fatty alcohols, fatty acids or polyol fatty acid partial esters, can be suitable hydrogen bond disruptors.

[0010] Among suitable hydrogen bond disruptors we have found that the following types of material are particularly suitable: carboxylic acids: including alkanoic carboxylic acids particularly C-| to C22. more particularly C4 to C-] 8- especially CQ to C-12. acids. Among these, the shorter chain, particularly C-_| to C4, acids - even though technically effective - are more volatile and have more noticeable smells and may thus be less desirable; and aryl carboxylic acids such as benzoic acid; alkyl amines, particularly C3 to C-|g. more particularly CQ to C-|2- especially C5 to C-| Q. alkyl amines. Amines having a (main) alkyl chain shorter than about 6 carbon atoms are relatively volatile and their odour may be considered disadvantageous. These may be primary, secondary or tertiary amines and among secondary and tertiary materials the other substituent groups may be alkyl e.g. C-| to C-|6 alkyl, but more usually C-] to Cg alkyl, group(s) or (poly)hydroxyalkyl groups particularly of the formula: -(CH_nH2_n+-|O)_m- where each n is independently from 2 to 4, usually 2 or 3 and desirably 2, and m is from 1 to 10, desirably from 1 to 5, or a combination of alkyl and (poly)hydroxyalkyl groups; carboxylic acid amides, particularly of C-| to C22 carboxylic acids. The carboxylic acids may be fatty acids (hydrocarbyl monocarboxylic acids) or dicarboxylic acids, particularly carbonic acid. Useful fatty acid amides are C-| to C22_> particularly Cg to C22. ^more particularly Cg to C20- fatty acid primary, secondary or tertiary amides. Useful carbonic acid amides are lower e.g. C-| to Cg, alkyl ureas, particularly tetra-alkyl ureas in which the alkyl groups can be the same or different but are desirably the same, e.g. tetra-methyl, -ethyl or -butyl ureas. In the secondary and tertiary amides the other substituent groups may be alkyl e.g. C-| to C-_|g alkyl, but more usually C-_| to

Cg alkyl, group(s), or (poly)hydroxyalkyl groups particularly of the formula: -(CH_nH2n+iO)_m- where each n is independently from 2 to 4, usually 2 or 3 and desirably 2, and m is from 1 to 10, desirably from 1 to 5, or a combination of alkyl and

(poly)hydroxyalkyl groups; ethers particularly aryl group ethers such as alkyl phenyl ethers; and polyethers, particularly polyoxyalkylene ethers e.g. polyethylene glycols, particularly those with and average of from 5 to 100, particularly 5 to 25, repeat units such as

PEG 300 and PEG 400; fatty alcohol polyalkoxylates, particularly those based on Cg to C20. especially Cg to C-|g, alcohols; fatty acid polyalkoxylates, particularly those based on Cg to C20_> especially Cg to C-|g, fatty acids; polyalkoxylates of polyol partial fatty acid esters, particularly of polyols such as glycerol, sorbitol or sorbitan, with Cg to C20- ^more particularly Cg to C-|g fatty acids; mixtures of two or more of the above materials or types of material.

[0011] The fatty acid tertiary C-| to Cg alkyl amides, such as di(lower) alkyl formamides, particularly dimethyl formamide, di(lower) alkyl acetamides, particularly dimethyl acetamide, and the C-_] to Cg tetra-alkyl ureas such as tetra-(lower alkyl) ureas, particularly tetra-methyl, - ethyl and -butyl urea, are dipolar aprotic materials and may have advantages when the formulations include materials that are sensitive to, or react with protic materials. Additionally, such materials, particularly the tetra-(lower alkyl) ureas may be especially beneficial where the end use demands require the use of relatively high melting or softening polyurethanes e.g. having melting temperatures above 100⁰C, particularly above 11O⁰C. In this context the melting temperature of the oligomer on its own appears to provide a reasonably good correspondence with the gel melting temperature of a structured oil including the structurant. The oligomer melting temperature can be measured by differential scanning calorimetry (dsc) - this class of oligomeric structurants show multiple endotherms on heating. A convenient way of assessing melting temperature is to take the temperature of the highest principal endotherm shown in the dsc trace. Relatively high gel melting temperatures in structured oil formulations are particularly desirably in dispersion concentrates of agrochemical actives to provide good formulation stability on high temperature storage. Desirable melting temperatures for such formulations may be above 4O⁰C, more desirably above 5O⁰C and particularly above 55⁰C.

[0012] The fatty alcohol, fatty acid and partial ester polyalkoxylates described above are desirably polyethoxylates, though mixed poly(eth/prop)oxylates may be used particularly where the molar proportion of propoxylate residues is not more than 25%, more usually not more than 10%. Further, desirably they have polyalkoxylate chains including 3 to 50, especially 5 to 30, alkoxylate residues. Polyethoxylates having 3 to 50, especially 5 to 30, alkoxylate residues are particularly useful.

[0013] The amount of the hydrogen bond disruptor incorporated with the structurant oligomer will usually be from 0.5 to 20, more usually 2 to 15, particularly 4 to 10, moles hydrogen bond disruptor per kg oligomer. The range of hydrogen bond disruptors described above vary widely in molecular weight so weight ratios and percentages can only be a very general guide, but usually the weight proportion of hydrogen bond disruptor will be from 10 to 200%, particularly 25 to 150%, especially 40 to 130%, by weight of the oligomer. [0014] The hydrogen bond disruptor is mixed with or incorporated into the structurant oligomer, typically at a suitably superambient temperature typically close to and usually above the melting temperature of the oligomeric structurant. The invention accordingly includes a method of making a combination of the invention which comprises mixing the oligomeric structurant and the hydrogen bond disruptor at a temperature above the melting temperature of the oligomeric structurant. Conveniently, the mixing can be carried out by co- melting the two materials. This is usually done at a suitable temperature from 70 to 18O⁰C₁ particularly 100 to 16O⁰C. We have not found need to protect the materials from oxidation or other degradation when testing on a small scale, but expect that on a commercial scale this will be done in a closed vessel, especially where the hydrogen bond disruptor is relatively volatile. Although preformed solid structurant oligomer can be (re)melted to enable mixing with the hydrogen bond disruptor, mixing can be carried out conveniently after synthesis of the structurant oligomer particularly as or immediately after the oligomer is discharged from the synthetic reaction vessel - typically as a melt, if necessary heating the mixture to facilitate mixing. The mixed product typically takes the form of a liquid or a paste. Desirably, particular combinations of hydrogen bond disruptor and structurant oligomer will be chosen to give mixed products that facilitate ease of handling, particularly incorporation into the oil. The mixed product typically takes the form of a liquid or a paste, usually a soft paste. [0015] The mixed product will typically be incorporated into the oil it is desired to structure by mixing it into the oil, using standard mixing techniques. It is a major advantage of this invention that this mixing can be carried out without needing to heat the oil up to close to the melting temperature of the polyurethane, and accordingly, desirably this mixing can be and desirably is carried out at temperatures which are much lower than might be otherwise possible and especially at ambient temperature. Moderately super-ambient temperatures e.g. up to 100⁰C, though desirably not more than 6O⁰C, particularly not more than 50⁰C, may be used, but are not believed to give any advantage and will add cost in heating the oil. [0016] As described in our earlier application, desirably the structured oil system of the invention uses oligomeric structurants (particularly as described in WO 2007/135384 A) which include a dimer component unit of the formula (I) below and/or a trimer component unit of the formula (III) below.

[0017] Oligomeric structurants including dimer units generally include a dimer component unit of the formula (I):

-(X)-(D)-(X)CO-NH-R¹- (I) where

-(D)- is a difunctional residue which is or includes fatty acid dimer residues; each X is independently -O- or -NH-, though usually the X groups are either both -O- or both -NH-; and

R¹ is a C-_| to Cso, particularly a C2 to C44 hydrocarbylene group.

[0018] More usually, the oligomeric structurant compounds used in the invention include repeat units of the formula (Ia):

-(X)-(D)-(X)C(O)NH-R¹-NHC(O)- (Ia) where D, R¹ and each (X) are independently as defined for formula (I).

[0019] In particular, repeat unit in the oligomers used in the invention can be urethane repeat units of the formula (Ib):

-0-(D)-OC(O)NH-R¹ -NHC(O)- (Ib) where D and R¹ are independently as defined for formula (I), or urea repeat units of the formula (Ic):

-NH-(D)-NHC(O)NH-R¹ -NHC(O)- (Ic) where D and R¹ are independently as defined for formula (I). [0020] Thus the overall oligomer can be of the formula (II):

R²-[(X)-(D)-(X)OCNH-R¹-NHCO]_m-(X)-(D)-(X)-R2 (||) where R¹ , (X) and -(D)- are each independently as defined for formula (I); each R2 is independently H, a group -C(O)R^, where R^ is a hydrocarbyl group, particularly a C-| to CSQ, more usually a C-| to C44, especially alkyl, group, or a group -C(O)NH-R¹ -NHC(O)-(X)-R⁴; or a group -C(O)NH-R⁴; or the group -(X)R² is a group -0(A0)_n-(C0)pR⁴, where each OA is independently an ethyleneoxy or propyleneoxy group, n is from 1 to 50, p is O or 1 ; where each R¹ and X are independently as defined above and each R⁴ is independently a hydrocarbyl group, particularly a C-_| to CQQ, more usually a C-| to C44, especially alkyl, group; and m is from 1 to 25. [0021] Within this formula, desirable polyurethane oligomers have the formula (Na):

R^2a-(X^a)-[(D^a)-O₂CNH-R^{1 a} -NHCO₂Im i-(D^a)-(X^a)-R^2a (^lla) where R^{1 a} is independently as defined for R¹ in formula (I); each -(D^a)- is independently the residue of a diol which is or includes fatty acid dimer diol residues; each R^2a is independently as defined for R² in formula (II); each X^a is independently as defined for X in formula (II); and ml is an average value of from 1 to 25, and desirable polyurea oligomers have the formula (lib):

R^2b-(X^bH(D^b)-NHCONH-R^{1 b}-NHCONH-]_m2-(D^b)-(X^b)-R^2b (H^b) where R^{1 b} is independently as defined for R¹ in formula (I); each -(D^b)- is independently the residue of a diamine which is or includes fatty acid dimer diamine residues; each R^2b is independently as defined for R² in formula (II); each X^b is independently as defined for in formula (II); and m2 is an average value of from 1 to 25.

[0022] Oligomeric structurants including trimer units generally include a trimer component unit of the formula (III):

-(X')₂-(T)-(X')CO-NH-R¹⁰- (III) where

-(T)- is a trifunctional residue which is or includes fatty acid trimer residues; each X' is independently -O- or -NH-, though within any component unit the X groups will usually be all either -O- or -NH-; and R¹O is independently a group as defined for R¹.

[0023] In particular trimer derived units within the formula (III) will be based on trimer triol and/or trimer triamine component units and the corresponding repeat units may be of the formula (Ilia):

-(X')- (T)(X¹R^{1 1}MW(O)NH-R¹⁰-NHC(O)- (Ilia) where T, R¹0 and each X' are independently as defined for formula (III) and

R^{1 1} is H, or (more usually) a group -C(O)NH-R¹², or a group -C(O)NH-R¹³-NHC(O)-

(forming a third link as part of the repeat unit); where

R¹² is a hydrocarbyl group, particularly a C-| to CQQ, more usually a C-| to C44, especially alkyl, group; and

R¹3 is a group as defined for R¹⁰ in formula (III).

[0024] In particular, repeat unit in the oligomers used in the invention can be urethane repeat units of the formula (IHb):

-0-(T)(OR^{1 1}J-OC(O)NH-R¹O-NHC(O)- (MIb) or urea repeat units of the formula (MIc):

-NH-(T)(OR^{1 1})-NHC(O)NH-R¹0-NHC(O)- (MIc) where T, R¹O and R^{1 1} are independently as defined for formula (III) or (IMa).

[0025] Oligomers used in the invention may include both dimer containing and trimer containing units (see also below on the dimer/trimer source materials).

[0026] The dimer and/or trimer units in the structurants used in the invention may be provided as residues of dimer and/or trimer acids respectively reacted with hydroxyl or amine ended oligourethane or oligourea units, for example as the products of chain extension reactions. In such cases dimer component units may be of the formula (IV):

-(OC)-(D')-(COX")-R²⁰- (IV) where

D¹ is the residue of a dimer acid less the (two) carboxyl groups; each X" is independently -O- or -NH- , though within any component unit the X groups will usually be all either -O- or -NH-; and

R²O is the residue of a urethane or urea oligomer, and dimer containing repeat units may be of the formula (IVa):

-(OC)-(D')-(COX")-R²⁰-(X")- (IVa) where D', each X" and R²O are independently as defined for formula (IV). [0027] Correspondingly trimer containing units may be of the formula (V):

-(X"C(O))₂-(T')-(COX")-R²⁰- (V) where each X" and R²⁰ are independently as defined for formula (IV) and T' is the residue of a trimer acid less the (three) carboxyl groups, and trimer containing repeat units may be of the formula (Va):

-(X"C(O))-(T)(COX"R²¹ )-(C(O)X")R²⁰- (Va) where D', X" and R²^ are as defined for formula (IV), and

R²¹ is H, or (more usually) a group -C(O)X"-R²², or a group -C(O)X"-R²³-X"C(O)-

(forming a third link as part of the repeat unit); where each X" is independently as defined for formula (IV);

R²² is a hydrocarbyl group, particularly a C-| to CQQ, more usually a C-| to C44, especially alkyl, group; and

R²³ is a group as defined for R¹0 in formula (III).

[0028] Although in such oligomers the oligourethane or oligourea units may include no such dimer or trimer residues, it is desirable that they do contain dimer and/or trimer residues (and will thus also fall within formula (II) above).

[0029] The oligomers can include mixed urethane and urea repeat units either by using a mixture of hydroxyl - diol or triol - and amine - diamine or triamine - or by including a hydroxy amine in the synthesis (see further below) and the end group (where it is other than H) can be linked by ester, urea or urethane links depending on whether the oligomer is hydroxyl, amine or isocyanate ended and correspondingly by using an alcohol, amine, isocyanate or fatty acid (or suitably reactive derivative) to provide the end group functionality. [0030] The term "structurant" describes a material which provides structure in the oil based formulations of the invention which improves the stability of the dispersion of the agrochemical active. Correspondingly in describing oil phases as "structured" we mean that solids dispersed in a structured oil phase show a much lower tendency to settle or segregate from the oil continuous phase than in the absence of the structurant. Generally the structure is provided by gelling the oil phase and it is usually possible to measure the yield stress of the gelled oils. The yield stress enables the gelled oil to provide support for dispersed agrochemical active thus stabilising the dispersions, with the suspended solids showing a reduced tendency to settle out of suspension or separate from the oil phase. It is possible (see further below) for the gel to be "amorphous" in which case it will not generally show a well defined yield stress, but it rheological properties provide support for the dispersed agrochemical. Generally, the structured oil based formulations of the invention show strongly shear thinning properties even at relatively low shear rates and this aids pouring or pumping of the structured oil based concentrate and its dilution in water. [0031] Oil dispersion agrochemical formulations, also known as "oil flowable", "oil concentrate", "oil suspension concentrate" and "non-aqueous suspension concentrate formulations, are concentrate formulations in which the agrochemical active is dispersed as solid particles in an oil phase. In this context the term oil is used to cover agrochemically acceptable non-aqueous organic liquids used as dispersion carrier fluids in such formulations. Many of these will be immiscible with water and conventionally regarded as "oils" e.g. mineral and other hydrocarbon oils and ester oils, some may be water miscible e.g. lower alkanols, or hydroxylic e.g. fatty alcohols, glycols or liquid polyols, or otherwise may not usually be thought of as oils. The term "oil" is used for such carrier fluids as a convenient term. Generally oil dispersion formulations are made so that they emulsify readily on dilution with water, desirably with just the agitation required to dilute the formulation. [0032] The products used in this invention are oligomers and/or oligomers which may have varying repeat units. For convenience the term oligomer is used to refer to such materials irrespective of the number of repeat units or molecular weight of the materials concerned.

[0033] The group -(D)- is a difunctional residue which is or includes residues based on fatty acid dimer residues. Fatty acid dimers (more commonly referred to simply as "dimer acids") are the well known mainly dimeric oligomerisation products derived from unsaturated fatty acids (industrially principally oleic, linoleic and/or linolenic acids), typically thermally oligomerised using clay catalysts. Generally they have average molecular weights corresponding to approximately two molecules of the starting fatty acid, so dimerised oleic acid has an average molecular weight corresponding to a nominally C35 diacid. As manufactured, dimer acids have unsaturation, typically corresponding to 1 or 2 ethylenic double bonds per molecule, but this may be reduced (hydrogenated) in making starting materials for the oligomers used in this invention.

[0034] The dimer derived starting materials will typically be either a dimer diol or a dimer diamine (or a mixture of these) (but see also below for description of chain extenders including dimer components). Dimer diols are the dihydroxy alcohols obtained by reducing or hydrogenating a dimer acid derivative, usually the methyl ester, to the dimer diol or by dimerisation of a corresponding unsaturated fatty alcohol. Dimer diamines are commercially made by nitrilation of the fatty acid e.g. with ammonia, followed by hydrogenation. For dimer derived residues, the group (D) will typically be either the residue of a dimer diol of the formula (Ilia) HO-(D)-OH, or a dimer diamine of the formula (MIb) H2N-(D)-NH2, i.e. after removal of the diol hydroxyl or diamine amino groups. Hydroxyl ended dimer components may also be provided by using hydroxyl ended dimer acid oliogoesters with diols. [0035] Dimer acids are commercially made as distillation fractions from the oligomerisation reaction described above and typically will include small proportions of monocarboxylic and tricarboxylic materials. The proportion of such monofunctional material is desirably kept relatively low as such compounds will give will tend to act as chain stoppers in the urethane or urea oligomers. Generally the proportion of residues of such monofunctional hydroxyl or amino compounds in the material used to make the oligomer will not be more than about 6 wt%, more usually not more than about 3 wt%, and desirably not more than about 1 wt%, of the total diol or diamine residues used. Amounts from 0.5 to 3 wt%, more usually 1 to 2 wt%, of the total diol or diamine residues used are typical. [0036] Trifunctional hydroxyl or amino compounds may be present in dimer acids and their derivatives used in this invention and such compounds will typically be incorporated into the oligomers and may give rise to branched oligomers. The proportion of residues of such trifunctional hydroxyl or amino compounds in the material used to make the oligomers used in the invention will not generally be more than about 80 wt%, more usually not more than about 25 wt%, and desirably not more than about 3 wt%, of the total diol or diamine residues used. Amounts from 0 to 2 wt%, of the total diol or diamine residues used are typical. [0037] Other difunctional compounds can be substituted for part of the dimer diol or diamine to modify the effect of the oligomer on the properties of the oil system, for example to vary the gel strength or improve the thermal stability i.e. increase the temperature at which the gel softens or melts.

[0038] Suitable such diols include alkane diols, e.g. 2 ethylhexane-1 ,3 diol, DD-alkane diols such as ethylene glycol, 1 ,3-propane diol and 1 ,4-butane diol, neopentyl glycol (2,2- dimethylpropane-1 ,3-diol), 1 ,6-hexane diol and 1 ,10-decane diol, polyalkylene glycols particularly those made using ethylene, propylene or butylene oxide, predominantly hydroxyl ended polyester polyol oligomers of dicarboxylic acids, such as adipic, azeleic, sebacic and dimer acids and their mixtures, and diols, such as those set out above (including dimer diols), partial fatty esters of polyols in which polyols such as glycerol, trimethylolpropane, sorbitol sorbitan, polyglycerol, pentaerithrytol and their alkoxylated versions, are esterified with fatty acids to give an average hydroxyl functionality close to 2, or such that two hydroxyl groups on the ester are substantially more reactive and fatty acids esters in which the fatty acids contributes hydroxyl functionality, such as glycol and polyol esters of ricinoleic acid, 12-hydroystearic acid and 9,10-dihyroxystearic acid. Diols from alkoxylation of ammonia, such as diethanolamine, or hydrocarbyl, particularly alkyl, especially fatty alkyl, amines such as laurylamineand diol derivatives of epoxidised oils and fats may also be used. [0039] Using such polymeric diols it is possible to control the molecular weight and relative hydrophobicity of the diol so it can be chosen to be similar or different to the dimer diol units. This may enable more subtle adjustment of the structuring effect of the oligomer on the oil system. When used, such other diols will generally be from 1 to 75 wt%, more usually from 3 to 50 wt%, and desirably from 5 to 20 wt%, of the total diol residues used. Correspondingly the proportion of dimer diol residues used will generally be from 25 to 99 wt%, more usually from 50 to 97 wt%, and desirably from 80 to 95 wt%, of the total diol residues used.

[0040] Amines that can substitute for dimer diamine include hydrocarbyl diamines particularly alkylene diamines such as ethylenediamine, 1 ,2- and 1 ,3-diaminopropane, 1 ,4-diaminobutane, 1 ,2-diamino-2-methylpropane, 1 ,3- and 1 ,5-diaminopentane, 2,2- dimethyl-1 ,3-propanediamine, 1 ,6-hexane-diamine (hexamethylenediamine), 2-methyl- 1 ,5-pentanediamine, 1 ,7-diaminoheptane, 1 ,8-diamino-octane, 2,5-dimethyl- 2,5-hexanediamine, 1 ,9-diaminononane, 1 ,10-diaminodecane and 1 ,12-diaminododecane, cyclic hydrocarbyl amines such as 4,4'-methylenebis(cyclohexylamine), 1 ,3- cyclohexanebis(methylamine), adamantane diamine and 1 ,8-diamino-p-menthane, aromatic diamines such as 1 ,2-, 1 ,3- and/or 1 ,4-phenylene diamine, 2,4,6-trimethyl- 1 ,3-phenylenediamine, 2,3,5,6-tetramethyl-1 ,4-phenylenediamine, xylene and naphthalene diamine (all isomers), diaminophenanthrene (all isomers, including 9,10), 2,7-diaminofluorene, diaminonaphthalene (all isomers, including 1,5; 1 ,8; and 2,3) and cyclic amines such as 4-amino-2,2,6,6-tetramethyl-piperidine. Such diamines may include hetero- e.g. oxygen, atoms particularly in alkyleneoxy residues. Examples of such materials include the so-called Jeffamine diamines (poly(alkyleneoxy)-diamines from Texaco). The diamines may include further nitrogen atoms as in polyalkylene amines, which are typically of the formula: NH2-(CH2CH2NH)_mCH2CH2-NH2, where m is from 1 to about 5 and examples include diethylenetriamine and triethylenetetramine. The further nitrogen atoms may also be present as tertiary nitrogen atoms in particular as hetero-atoms in a cyclic group as in bis(aminoethyl)-N,N'-piperazine and bis(aminopropyl)-N,N'-piperazine. Such diamines may have one primary amine group and one secondary amine group as in N-ethylethylenediamine or 1-(2-aminoethyl)piperazine.

[0041] Generally when such modifying diamines are included the amounts will be relatively small as the diamines will react to give (bis)-urea linkages that will lead to stiffer chains and the oligomers will usually have higher melting temperatures. When used, such other diamines will generally be from 1 to 20 wt%, more usually from 1 to 15 wt%, and desirably from 1 to 10 wt%, of the total diamine residues used. Correspondingly the proportion of dimer diamine residues used will generally be from 80 to 99 wt%, more usually from 85 to 99 wt%, and desirably from 90 to 99 wt%, of the total diamine residues used. [0042] It is possible to include materials that provide both amino and hydroxyl functionality, which will generate both urethane and urea linkages in the product oligomer and examples include mono- and di- ethanolamine and propanolamine, 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 4-amino-1-butanol , 2-amino-2-ethyl-1 ,3-propanediol, AMPD(2-amino-2-methyl-1 ,3-propanediol), 2-amino-2-methyl-1 ,3-propanediol, and 2-amino-2-hydroxymethyl-1 ,3-propane-diol. [0043] It is also possible, though not particularly desired to combine such other diols with dimer diamine and other amines with dimer diol to give mixed urethane/urea oligomers. [0044] Tri- and higher functional hydroxyl and/or amino functional components can be included in the reagents used to make the structurant oligomers. Generally the proportions used will be small e.g. similar to the amounts of non-dimer amines (see above), and mono- or di- functional hydroxy or amino functional (or additional monocarboxylic functional) components may be included to act as chain stoppers to control the overall molecular weight and/or the extent of branching and/or crosslinking to avoid producing intractable and/or oil insoluble oligomers.

[0045] Chain extension reactions are briefly mentioned above as a way of making oligomeric structurants useful in the present invention, particularly by using multifunctional reagents to link together smaller oligomer units with possible subsequent reaction to end-cap the products. The chain extension reactions can form urethane/urea linkages, for example by reaction of hydroxyl/amine ended oligomer units with isocyanate chain extenders, or of isocyanate ended oligomer units with hydroxyl/amine ended chain extenders; or ester or amide linkages for example by reaction of hydroxyl/amine ended oligomer units with carboxyl ended chain extenders. The oligomer units used in this approach to the synthesis of oligomeric structurants, are urethane and/or urea linked oligomers made from suitable monomer materials such as those described above. The oligomer units can, and usually will, include dimer and/or trimer component residues, in which case the chain extender(s) can be di-, tri- or higher functional reagents which will typically be low molecular weight materials. In contrast, oligomer fragments which do not include dimer and/or trimer component residues may be used in which case the chain extender(s) will include dimer and/or trimer component residues e.g. using hydroxyl, amine, isocyanate or acid functional dimer or trimer compounds as appropriate. Of course, where the oligomer fragments do include dimer and/or trimer component residues, dimer or trimer based chain extender(s) may also be used. [0046] Generally the proportion of chain extending agent will be chose to be appropriate to provide an oligomer product having a desired molecular weight, higher than that of the oligomer unit(s). The weight percentages will thus depend on the molecular weight of the oligomer units and of the chain extender. When trimer acid is used as the chain extender amounts of from 1 to 40%, more usually from 3 to 30%, particularly 5 to 20% by weight of the oligomer which is being chain extended, will be typical, with similar weight proportions for other trimer based chain extenders and corresponding amounts for chain extenders of different molecular weight and functionality. As with the tri- and higher functional hydroxyl and/or amino functional components mentioned above, mono-functional components may be included to act as chain stoppers to control the overall molecular weight and/or the extent of branching and/or crosslinking. End capping may be carried out after chain extension along the lines described above, though the inclusion of monofunctional components as chain stoppers many make separate end capping unnecessary. We have found that using trimer based chain extenders, particularly with dimer based oligomeric units can give structurants which give structured oils having a reduced tendency to "bleed" (syneresis) and good thermal stability.

[0047] The group R¹ in formula (II) and corresponding groups in other formulae, is a C-_| to Ceo- more usually a C2 to C44, particularly a C4 to C36, especially a C4 to C24, hydrocarbylene group. Synthetically it can be considered as be the residue left after removal of an, and usually two, isocyanate groups from the (di-)isocyanate starting material (see below for oligomer synthesis). Suitable isocyanates include aromatic isocyanates, particularly diisocyanates e.g. phenyl diisocyanate, methylene bis-(4,4')-phenyl isocyanate (also known as diphenylmethane-4,4'-diisocyanate or MDI), toluene diisocyanate (TDI), tetramethylxylene diisocyanate or derivatives and variants of such materials for example modified MDI; but more usually non-aromatic diisoycanates such as alicyclic isocyanates, particularly diisocyanates e.g. methylene bis-(4,4')-cyclohexyl isocyanate (4,4'- dicyclohexylmethane diisocyanate), or isophorone diisocyanate; dimer diisocyanate; or, and particularly, alkylene isocyanates, particularly diisocyanates, more particularly C2 to C-] 2, especially C2 to CQ, and desirably C2 to Cg alkylene, diisocyanates, such as 2,2,4-trimethyl-

1 ,6-hexamethylene diisocyanate; and desirably diisocyanates of the formula: OCN-(CH2)p-NCO where p is from 2 to 12, more particularly from 2 to 8, and especially from

2 to 6 e.g. 1 ,12-dodecane diisocyanate or 1 ,6 hexamethylene isocyanate.

[0048] The groups R^, in formula (II) and corresponding groups in other formulae, when other than H, provide end groups for the oligomer. Where the oligomers are end capped, the end cap groups, designated by -C(O)R³ , -(X)-R⁴ in the group -C(O)NH-R¹ -NHC(O)-(X)-R⁴, -C(O)NH-R⁴ and -O(AO)_n-(CO)_pR⁴ in formula (II), can be acyl groups, as in R³C(O)-, or hydrocarbyl, as R⁴ in the group -(X)-R⁴, in the group -C(O)NH-R⁴ or in the group -C(O)NH-R⁴, (where -(X)-, R¹ , R⁴, R⁵, AO, n and p are as defined in formula (II) above) the groups R³ or R⁴ are independently C-| to Cgrj. more usually a C-| to C44, desirably a C-| to C24, hydrocarbyl, especially alkyl or alkenyl groups.

[0049] When the end cap group is a hydrocarbyl group (R⁴) it may be straight or branched chain, open chain or cyclic (including polycyclic), saturated or unsaturated group and is particularly an alkyl or alkenyl group such as stearyl, isostearyl, oleyl, cetyl, behenyl, e.g. as derived from the linear alcohols available under the commercial designations "Nafol" and "Nacol", the mixtures of linear and branched chain alcohols commercially available as "LJaIs"; or as derived from Guerbet (branched chain) alcohols e.g. those commercially available under the "Isofol" commercial designations or a cyclic, particularly acyclic, group such as cyclohexyl, or a polycyclic group such as the residue or rosin alcohol for example as derived from Abitol-E from Eastman. Hydrocarbyl end caps can be linked to the oligomeric chain by -O- groups (giving a urethane link) or by -NH- groups (giving a urea link) and a terminal (bis-)isocyanate derived residue.

[0050] When R^ is an acyl group the group R³ is usually a C-j to C59 group and more usually is a long chain particularly a C7 to C43 group, more particularly a Cg to C31 and especially a C-_| 1 to C23 hydrocarbyl group which may be straight or branched chain, open chain or cyclic (including polycyclic), saturated or unsaturated and is desirably an alkyl, alkenyl or alkadienyl group. In other words, R^ is part of an acyl group derived from the corresponding C2 to Csrj. particularly CQ to C44, more particularly a C<|rj to C32 and especially a C-12 ^to ^24- f^{attv ac}^- 'ⁿ particular the acyl group -C(O)R^ is derived from a Ce to C30 fatty acid, particularly lauric, stearic, isostearic, oleic or erucic acids. Other monofunctional acids that can be used include cyclic, particularly acyclic, e.g. polycyclic, acids such as abietic acid (rosin acid). Acyl end caps can be linked to the oligomeric chain by -O- groups (giving an ester link) or by -NH- groups (giving an amide link). [0051] The oligomers used in this invention desirably have a number average molecular weight of from 1000 to 20000, more usually from 1500 to 10000 and particularly from 2000 to 8000. For compounds of the formula (II), this corresponds to (average) values for the index m, including the indices ml and m2 in formulae (Na) and (lib) respectively, of typically from 1 to 20 more usually from 2 to 15 and particularly from 2 to 10 urethane dimer diol oligomer repeat units i.e. the value of the index m, per molecule. Similar numbers of repeat units will be typical for trimer based and other structurant oligomers used in the invention. [0052] Although trifunctional starting materials may be used, when these are present care may be needed to avoid making insoluble or intractable oligomers arising from excessive crosslinking. At least to some extent, the average functionality can be controlled by including non-dimer difunctional reagents in a similar way to those described above with dimer derived OH or NH2 functional materials and/or monofunctional regents e.g. monofunctional alcohols or amines, may be included as chain stoppers. We have made oligomers that are effective gelling agents using trimer triol as a starting material or by using trifunctional chain extenders such as trimer acid (see below) without having to include monofunctional chain stoppers.

[0053] The oligomers used in this invention, particular oligomers including repeat units based on dimer and trimer units as described above with reference to formulae (I) to (V) above can be made by generally conventional methods. At least notionally, the reactions can be considered as a first stage forming an intermediate oligomer and subsequently, if desired, reacting capping groups onto the intermediate oligomer. The intermediate oligomer can be hydroxyl (diol or triol) or amine (diamine or triamine) ended or isocyanate ended depending in particular on the molar ratio of the starting diol or amine and isocyanate (noting that isocyanate ended oligomers will not usually be left uncapped in view of the reactivity of isocyanate groups). [0054] Thus polyurethanes of the formula (Na) can be made by reacting a diol of the formula: HO-(D^a)-OH, where -(D^a)- is as defined in formula (Na), with a suitable diisocyanate, particularly of the formula OCN-R¹-NCO, where R¹ is as defined for formula (I), under urethane polymerisation conditions, particularly in the presence of a urethane polymerisation catalyst (see also below), to form the intermediate oligomer. Corresponding reactions can be used to make trimer containing materials. [0055] End caps may be reacted on depending on the groups at the end of the oligomer. Where the oligomer is isocyanate ended, reaction with an alcohol R²OH, where R² is as defined in formula (II), will give a R² substituted urethane ended oligomer and reaction with an amine R²NH2, where R² is as defined in formula (II), will give a R² substituted urea ended oligomer. Where the oligomer is hydroxyl (diol) ended, the capping reaction may be with an alcohol of the formula: R²OH (or a reactive derivative), where R² is as defined in formula (II), under etherification conditions, particularly in the presence of an etherification catalyst such as potassium carbonate, potassium hydroxide, sodium hydroxide or stannous octoate, or an acid of the formula R^COOH (or a reactive derivative), where R^ is as defined for formula (II), under esterification conditions, particularly in the presence of an esterification catalyst such as tetrabutyl titanate (TBT), tetra-isopropyl titanate (TIPT), stannous octoate e.g. the commercial product Tegokat 129, bases e.g. potassium or sodium carbonate, acids e.g. para-toluene sulphonic acid (PTSA), dodecyl benzene sulphonic acid (DBSA) or sulphuric acid, more particularly by reacting with an ester of the formula R^COOR^, where R3 is as defined for formula (II), and R⁵ is a lower, particularly C-| to CQ, alkyl and especially a methyl, group under transesterification conditions, particularly in the presence of transesterification catalyst such as TBT, TIPT , stannous octoate, or a base e.g. potassium or sodium carbonate. [0056] Similarly polyureas of the formula (Mb) can be made by reacting a dimer diamine of the formula H2N-(D^b)-NH2, where -(D*⁵)- is as defined in formula (Mb), with a suitable diisocyanate, particularly of the formula OCN-R¹-NCO where R¹ is as defined for formula (I), under polyurea polymerisation conditions, particularly in the presence of a polyurea polymerisation catalyst (see also below), to form the intermediate oligomer. Corresponding reactions can be used to make trimer containing materials. [0057] End caps may be reacted on depending on the groups at the end of the oligomer.

Where the oligomer is isocyanate ended, reaction with an alcohol R²^OH, where R^2b is as defined in formula (lib), will give a R^2D substituted urethane ended oligomer and reaction with an amine R^2bNH2, where R^2b is as defined in formula (Mb), will give a R^2b substituted urea ended oligomer. Where the oligomer is amine (diamine) ended, the capping reaction may be with an acid of the formula R^COOH (or a reactive derivative), where R^ is as defined for formula (M), under amidation conditions, particularly in the presence of an amidation catalyst such as TBT, TIPT, E-cat (Tiθ2 with small amounts of TiCl4 Ti(OH)2 and

TiC^), more particularly by reacting with an ester of the formula R^COOR^, where R^ is as defined for formula (M), and R⁵ is a lower, particularly C-) to Cs, alkyl and especially a methyl, group under transamidation conditions, particularly in the presence of transamidation catalyst such as the amidation catalysts listed above.

[0058] From formula (II) the group R² used as an end cap may be the residue of a mono- alkyl or ester capped alkoxylate e.g. propylene glycol monoesters such as the isostearate, and the term "alcohol" for R²OH as used above is generic to include this as well as simple alcohols.

[0059] Catalysts for the urethane and urea reactions can be tertiary bases, e.g. bis- (N,N'-dimethylamino)-diethyl ether, dimethylaminocyclohexane, N,N-dimethylbenzyl amine, N-methyl morpholine, reaction products of dialkyl-(b-hydroxyethyl)-amine with monoisocyanates, esterification products of dialkyl-(b-hydroxyethyl)-amine and dicarboxylic acids, and 1 ,4-diaminobicyclo-(2.2.2)-octane, and non-basic substances such as metal compounds e.g. iron pentacarbonyl, iron acetyl acetonate, tin(ll) (2-ethylhexoate), dibutyl tin dilaurate, molybdenum glycolate, stannous octoate, TBT and TIPT. [0060] Generally where the intermediate oligomer is (or would be) hydroxy or amine ended, the reaction will generally be carried out in two stages, first formation of the intermediate oligomer and then capping the oligomer (if desired). Where the intermediate oligomer is (or would be) isocyanate ended, and particularly where the capping groups are hydroxyl compounds (alcohols) the reaction may be carried out in a single step by with all the reagents in a single vessel from the outset.

[0061] Where the synthesis includes chain extension reactions, these will usually be urethane or urea forming reactions (between isocyanate and hydroxyl or amine respectively) or ester or amide forming reactions (between carboxylic acid (or reactive derivative) and hydroxyl or amine respectively) and will be carried out under conditions described above for such reactions.

[0062] We have generally found it practical to carry out the synthetic reactions without solvent or diluent using the raw materials neat. In particular reagents such as monocarboxylic acid esters included as end capping reagents can act also as reaction diluents/solvents until they are reacted into the oligomers. However, it is possible to use solvents or diluents if desired to improve the ease of handling of the oligomer. Suitable solvents or diluents include acetone, toluene, plasticizer esters, other esters such as benzoates e.g. 2-ethylhexyl benzoate, or isopropyl esters such as ispropyl myristate, glyceride esters such as triglycerides e.g. glycerol trioleate, optionally (partial) esters of polyols, N-methylpyrrolidone, oils and carbonates.

[0063] Reactions with isocyanates, oligomerisation or capping reactions, are generally carried out at temperatures from 50 to 150⁰C, more usually 60 to 125⁰C. Reactions with acids or esters to form ester or amide end caps with acids are generally carried out at temperatures from 150 to 270⁰C, more usually 180 to 23O⁰C, e.g. at about 225⁰C. For both direct and trans- esterification and amidation reactions can be carried out at ambient pressure or at moderate vacuum e.g. from 600 to 10 mBar (60 to 1 kPa) gauge will usually be used. Inert gas e.g. nitrogen, sparging may be used under ambient or reduced pressure to aid removal of volatiles from the reaction. Generally, a small excess of the acid or the ester (usually a methyl ester) will be used.

[0064] A wide range of oils (carrier fluids) can be structured using the compounds of the invention and the best such compounds will provide structuring in a wide range of oils (rather than a relatively narrow range for each structuring compound). The range of oil polarity for which structuring can be provided is wide ranging from non-polar oils such as paraffinic oils to alkoxylate oils. Typical oils that can be structured using the formulated structurants of the invention include: liquid and low-melting temperature alcohols including relatively short chain alkanols such as Nbutanol and pentanol, medium chain alcohols such as 2-ethylhexanol and 2-ethyl- 1 ,3 hexanediol, long chain alcohols such as isodecanol, isotridecanol, cetyl alcohol, oleyl alcohol, octyldodecanol, liquid Cø to C32 alcohols e.g. Guerbet alcohols such as lsofol 24; liquid polyols such as glycols and (poly)glycerol; aromatic alcohols such as benzyl alcohol; polycyclic alcohols such as abietyl alcohol; branched liquid fatty alcohols, particularly Guerbet alcohols e.g. octyldodecanol or isostearyl alcohol (see above) e.g. the isostearyl alcohol available from Uniqema (now part of the Croda group) under the tradename Prisorine 3515; ester oils particularly those based on C2 to C30 linear, branched or unsaturated fatty acids and linear, branched or unsaturated fatty alcohols, and typically esters derived from monocarboxylic acid(s) with monohydric alcohol(s); di- or tri-carboxylic acid(s) with monohydric alcohol(s); or di- or poly-hydric alcohol(s) with monocarboxylic acid(s), e.g. the glycerol tris-2-ethylhexanoate ester oil available from Uniqema under the tradename Estol 3609, the isopropyl isostearate oil available from Uniqema under the tradename Prisorine 2021 , the methyl oleate oil available from Uniqema under the tradename Priolube 1400, methyl caprylate, synthetic triglyceride esters such as glycerol W-(Ce ^to C24)^{ates e}-9- glycerol tricaprylate such as Estasan 3596, glyceryl trioleate such as Priolube 1435, both available from Uniqema, and glycerol tri ricinoleate, PEG oleate and isostearate, isopropyl laurate or isostearate, trimethylpropane triesters e.g. with mixed CS/C-I Q. stearic or oleic acids; natural triglycerides such as rape seed (canola) oil, soya oil, sunflower oil and fish oil; methylated natural triglycerides such as methylated rape seed, soya and/or sunflower oils; aromatic ester oils, particularly esters of benzoic acid and Cø to C-|8 monohydric alcohol(s) e.g. the C-12 ^to C15 benzoate oil from Finetex under the tradename Finsolve TN; branched liquid fatty alcohols, particularly Guerbet alcohols e.g. octyldodecanol or isostearyl alcohol (see above) e.g. the isostearyl alcohol available from Uniqema under the tradename Prisorine 3515; branched liquid fatty acids, particularly isostearic acid and dimer acid (dimerised fatty acids, particularly oleic and/or linoleic acids), such as dilinoleic acid; and hydrocarbons including toluene, xylene, and liquid paraffinic materials such as hexane, octane, gasoline, diesel, liquid hydrocarbon waxes, lamp oil, paraffinic oils such as Sunspray 6N, 8N and 11N from Sunoco and Puccini 19P from Q8, (iso)-paraffinic oils such as lsopar V and Exxol D140 from ExxonMobil, and aromatic mineral oils such as the alkyl benzenes available from ExxonMobil under the Solvesso brand; miscellaneous liquids such as isophorone (3,3,5-trimethyl-2-cyclohexene-1-one), liquid (at

25⁰C); mixtures of more than one oil from the above types.

[0065] The liquids (for convenience referred to generically as "oils), particularly as set out above can be used as mixtures of two or more different types of oils. [0066] Of course, in agrochemical dispersions where the formulation is an oil based suspension of an agrochemical active, it follows that the oil will not be a solvent for the dispersed active, so the choice of oil will complement the desired active(s) in any particular formulation.

[0067] The amount of the oligomeric structurant used is typically from 0.2 to 15%, more usually from 0.5 to 10% and especially from 1 to 5%, by weight based on the total formulation. The oligomers may be used as the only structurants or, if desired in combination with other structurants, particularly to ensure that the desired structuring effect it achieved across the entire temperature range required for a particular product. When used with other structurants, the proportion of structurant of the invention will generally be from 25 to 95%, more usually from 40 to 80%, by weight of the total structurant used. The total amount of structurant when mixtures are used will generally be within the ranges given above for the compounds of the invention.

[0068] The structured oils can be used in a variety of applications particularly where dispersions in oils or water in oil emulsions are used including agrochemical formulations, particularly dispersions (see further below), paints, paint stripper formulations, emulsion explosives, inks and hard surface cleaners.

[0069] Agrochemical formulations in which formulations of the present invention can be applied are particularly so-called oil flowable formulations in which a solid agrochemical acitive is suspended in the structured oil, which forms an emulsion on dilution in water for spraying. To this end the oil flowable formulation will generally include surfactants, particularly appropriate (to the oil) oil in water emulsifiers.

[0070] The oil flowable formulations of the invention can include a wide range of agrochemical active materials and specifically, the active component of the formulation may be one or more plant growth regulators, herbicides, and/or pesticides, for example insecticides, fungicides, acaricides, nematocides, miticides, rodenticides, bactericides, molluscicides and bird repellants. Within this broad range, as is noted above, oil flowable compositions will typically include agrochemical actives which are insoluble in the oil used in the formulation. Given this, active ingredients which can be incorporated into oil based formulations of the invention include fungicides; insecticides; acaricides; nematocides and herbicides, particularly those listed in WO 2007/135384 A.

[0071] Formulations may be made up as oil dispersions of oil insoluble active(s) with further active(s) dissolved in the oil phase, usually so that on dilution the spray formulation is a suspoemulsion.

[0072] The active will generally be included in the OD formulation at a concentration of from 0.5 to 30%, more usually from 1 to 20%, and desirably from 2.5 to 10%, by weight of the formulation.

[0073] Surfactants are commonly included in OD formulations in particular to (a) aid dispersion of the active in the oil; and (b) incorporate emulsifier to promote ready emulsification of the oil flowable on dilution with water prior to spraying. For both purposes, it is desirable to use surfactants that are either soluble or dispersible in the oil and thus the choice of surfactant in any particular case will depend on the oil used. [0074] Surfactants which may be included to aid dispersion of the active in the oil include polymeric dispersants such as those available from Uniqema, including polyhydroxyester, particularly poly(hydroxystearic) acid such as Atlox LP-1 ; ABA polyhydroxyester-PEG-polyhydroxyester copolymers such as Hypermer B-246 and Zephrym PD 2206; polyamine modified polyesters such as Atlox LP-6; and alkyd type copolyesters such as Atlox 4914. With such dispersant surfactants, the amount included in an oil flowable formulation will typically be from 1 to 25, more usually from 2.5 to 15, and desirably from 2.5 to 12.5, weight % of the total formulation.

[0075] Surfactants which may be included as emulsifiers to promote ready emulsification of the oil flowable on dilution with water prior to spraying include anionic surfactants particularly sulphonated hydrocarbon surfactants e.g. alkylbenzene sulphonates, particularly as salts such as alkaline earth metal e.g. calcium, salts particularly calcium didodecylbenzene sulphonate; and non-ionic surfactants including block copolymer polyalkoxylates such as those sold under the tradenames Synperonic PE and Atlas G-5000; alkoxylated, particularly ethoxylated fatty alcohols such as those sold under the tradenames Synperonic A and Synperonic 13; sorbitan esters such as those sold under the tradename Span; ethoxylated sorbitan esters such as those sold under the tradename Tween; and ethoxylated sorbitol esters such as POE(40) sorbitol septaoleate such as that sold under the tradename Arlatone T(V) or POE (50) sorbitol hexaoleate such as that sold under the tradename Atlas G-1096 both from Uniqema. With such emulsifier surfactants, the amount included in an oil flowable formulation will typically be from 1 to 25, more usually from 2.5 to 15, and desirably from 2.5 to 12.5, weight % of the oil used in total formulation. [0076] Typically the total surfactant loading including dispersants for the suspended actives and emulsifiers for the oil will be from 5 to 35, more usually from 10 to 20, and desirably from 5 to 15, weight % of the total formulation.

[0077] Different types of oils may require different types of surfactant. Thus, for agrochemical formulations based on oils as follows (illustrated with surfactants commercially available from Uniqema): triglyceride oils - combinations of non-ionic surfactants such as esters of ethoxylated polyols e.g. POE (50) sorbitol hexaoleate (Atlas G-1096) or POE(40) sorbitol septaoleate (Arlatone T(V)), alkyd type copolyesters (Atlox 4914) and anionic surfactants such as alkyl aryl sulphonates usually in salt form such as amine e.g. the isopropylamine alkyl aryl sulphonate Zephrym 3300B; commonly in further in combination with polymeric surfactants such as Atlox polymeric surfactants, or block copolymeric alkoxylates such as Atlas G-5000; methylated oils - typically use combinations of anionic surfactants such as alkyl aryl sulphonates usually in salt form such as alkali or alkali earth metal salts e.g. the calcium alkyl aryl sulphonate Atlox 4838B (dissolved in ethylhexanol), in combination with a non ionic surfactant such as a fatty alcohol ethoxylates such as C-J2-15 3 ^{to 20} ethoxylates e.g. Synperonic series especially A3, A7, A11 , A20, or block copolymeric alkoxylates such as Atlas G-5000; ester oils such as lower alkyl, particularly methyl esters e.g. methyl oleate, - typically use combinations of non-ionic surfactants, particularly alcohol ethoxylates usually having relatively high HLB values e.g. Synperonic A20, and block copolymeric alkoxylates such as Atlas G-5000 (A-B block) and Synperonic PE105 (A-B-A block), with anionic surfactants such as alkyl aryl sulphonates, particularly linear alkyl benzene sulphonates such as dodecyl benzene sulphonate, especially as calcium salts; mineral oils - combinations of non-ionic surfactants, particularly polyol esters such as sorbitan esters e.g. Span series sorbitan esters particularly Span 80 sorbitan oleate, ethoxylated sorbitan esters e.g. Tween series ethoxylated sorbitan esters particularly Tween 85 POE 20 sorbitan trioleate, and alkyl alkyl sulphonates such as Zephrym 3300B; isoparaffinic oils - esters of ethoxylated polyols e.g. POE (40) sorbitol hexaoleate such as Atlas G-1086 or POE (50) sorbitol hexaoleate such as Atlas G-1096, or block copolymeric alkoxylates such as Atlas G-5000, usually in combination with anionic surfactants such as alkyl aryl sulphonates e.g. Atlox 4838B; aromatic base oils - typically use combinations of non-ionic surfactants, particularly alcohol ethoxylates usually having relatively high HLB values e.g. Synperonic A20, and block copolymeric alkoxylates such as Atlas G-5000 with anionic surfactants such as alkyl aryl sulphonates, particularly linear alkyl benzene sulphonates such as dodecyl benzene sulphonate, especially as calcium salts. [0078] The surfactants used may influence the performance of the structurant, and some improve it. Thus, for example in formulations based on paraffinic oils such as Puccini 19P from Q8, we have found that inclusion of a surfactant combination such as a sorbitan ester (Span 80 sorbitan oleate), an ethoxylated sorbitan ester (Tween 85 POE 20 sorbitan trioleate) and an aryl alkyl sulphonate (Zephrym 3300B) seems to improve the compatibility of the oligomeric structurant with the oil formulation and improves the structuring behaviour as compared with the absence of the surfactants. In general, the ability of the oligomer to provide structuring in oil based formulations seems to be broadly independent of the exact chemical nature of the surfactants used. In other words the formulations of the invention are robust to the presence of and variation of surfactants.

[0079] Optionally, an inert solvent and/or plasticiser can be added to the oligomer to improve handling and/or reduce melting temperature of the oligomer. The rheological properties of the structured oil phase can also be modified by addition of solvents and this can be used to modify the rheological properties of the formulation. Examples of solvents which are especially effective in reducing melting range include, 1-phenoxy-2-propanol, 3,7- dimethyl-6-octen-1-ol beta citronellol, 3,7-di-methyl-2,6-octadien-1-ol, 3-hexen-1-ol, cyclohexanone, ethylene glycol monopropyl ether, 2-ethyl-1-hexanol, 1-pentanol, propylene glycol monopropyl ether, 2,4,4-trimethyl-i-pentanol, cyclo-hexanol, hexyl alcohol, ethylene glycol monoisopropyl ether. When used the amount of solvent will generally be used at a proportion of from 10 to 90 %, more usually from 40 to 75 %, by weight based on the oligomer, representing from 0.5 to 45 %, more usually from 1 to 10 %, by weight based on the overall formulation.

[0080] The formulations may include othercomponents such as dispersants, electrolytes, wetters and similar materials that are commonly included in OD formulations. [0081] Overall the agrochemical formulations of the invention generally have compositions falling within the following ranges:

Amount (% by weight) Material

Broad Specific Preferred

Oil 10 to 95 20 to 90 40 to 80

Active 0.5 to 30 1 to 20 2.5 to 10

Structurant 0.1 to 15 0.2 to 10 0.5 to 5

Total Surfactant (when present) 5 to 35 10 to 20 5 to 15

Dispersant 1 to 25 2.5 to 15 2.5 to 12.5

Emulsifier 1 to 25 2.5 to 15 2.5 to 12.5 Solvent (when present) 0.1 to 45 0.2 to 30 0.5 to 15

Total 100 100 100

The oil based formulations of the invention are structured typically to provide dispersion stability desirably without making the oil based formulation so viscous that mixing of the oil based formulation particularly with water to form a spray mix becomes difficult. Mixing difficulties can arise in two ways, if the oil based formulation is sufficiently viscous that removing it from its storage container becomes difficult or if its viscosity make mixing with the dilution water slow or inefficient. This means that the desirable rheology for the structured oil based formulations of the invention is a gel which is readily shear thinning so that it readily becomes pourable and/or pumpable and/or spreadable e.g. brushable or sprayable (as for paints), but which is structured so as to provide improved dispersion of the solids in the diepsersion. Generally the structured formulations of the invention have a viscosity at low shear e.g. ca 10 s^'1 , of from 250 to 3000 mPa.s and thin down at higher shear so that the viscosity of the formulation during mixing with dilution water is typically from 100 to 500 mPa.s (substantially higher viscosities might inhibit efficient mixing with the dilution water). [0082] Particularly for agrochemical formulations, it is desirable that the structured oil based formulations should remain stably structured at ambient temperature for at least 1 month and at elevated temperatures typically up to at least 4O⁰C and desirably up to 5O⁰C₁ for at least 2 weeks and at subambient temperatures usually at least as low as O⁰C and more usually down to -1O⁰C and desirably as low as -17.7⁰C (O⁰F) for up to eight weeks. These performance requirements are desirably also met when the formulations include surfactants, and solvents (when present) as well as suspended solids. It is also desirable to have freeze thaw stability over at least 3 test cycles.

[0083] The structured formulations of the present invention are generally gels in which the dispersion of solids e.g. agrochemical active, is stabilised by the structured and desirably gel, nature of the concentrate. It is advantageous that the oligomer structurants can provide structuring over a wide range of oil polarity, thus enabling the selection of a suitable (non- solvent) oil for widely differing actives that it is desired to formulate as ODs, and to give structured dispersions that are stable over a range of thermal conditions appropriate to storage and use of the agrochemical formulations, the structuring is linked with good shear thinning properties that simplify dilution and thus making up spray formulations for practical application. It is particularly advantageous that the structuring is stable in the presence of useful concentrations of surfactants e.g. those typically used in agrochemical OD formulations. Further as manufacture of the oligomers does not necessarily use solvent, solvent, especially volatile solvent, free formulations can be made. [0084] Typically, oil based formulations of the invention including structurant, usually surfactant and suspended solid e.g. agrochemical active, can be readily emulsified by simple mixing with diluent water to give stable emulsions with the base oil as the dispersed phase in the dilution water. This is important in agrochemical applications where the resulting aqueous formulation, usually an emulsion of the oil with an agochemical active suspended in the oil discontinuous phase, is sprayed on vegetation, usually a crop and or weeds, or the ground adjacent to the crops to provide the desired agrochemical effect. Of course if a further active is included dissolved in the oil, the diluted formulation will naturally be a suspoemulsion formulation. Typically the rate of dilution with water for such formulations will be from 10 to 10000, more usually 10 to 1000 e.g. 20 to 100, fold by volume. The dilution water does not need to be soft; we have used water having a standard hardness up to 1000 ppm Ca^⁺ to dilute structured oil formulations successfully.

[0085] The invention thus includes a method of making a diluted agrochemical formulation for spraying (spray tank mix) which includes mixing in any order: a) an oil based formulations of the invention, desirably including at least one emulsifier surfactant; and b) water, particularly in an amount of from 20 to 100 times by volume of component a; to form a diluted agrochemical formulation.

[0086] We have observed that the structured oil based systems of and used in this invention are moderately sticky and in diluted agrochemical spray formulations this may enhance the adhesion of agrochemical components onto the substrate to be treated e.g. a plant or a pest such as an insect. [0087] Typically agrochemical oil flowable formulations will be applied at a rate of from

100 to 400 l(spray).ha"¹(crop treated), usually about 300 l.ha'^"' corresponding to application rates of the oil based concentrate (oil flowable) of from 1 to 20, more usually from 2 to 10 and desirably from 2 to 7 l(oil flowable concentrate). ha'1 (crop treated). The amount of active applied will depend on the potency of the active and the desired effect. [0088] The agrochemical spray formulations made by diluting the oil based formulations of the invention will normally be used to apply agrochemicals to vegetation or the ground adjacent to vegetation and accordingly the invention includes a method of treating vegetation in which the vegetation or the ground adjacent to vegetation is sprayed by a formulation of the invention, particularly a diluted formulation of the invention.

[0089] A further end use of the structurant / hydrogen bond disruptor combinations of the invention is in oil based paint stripper and similar formulations where the inclusion of a structurant enables much linger residence times on non-horizontal, particularly vertical, surfaces by inhibiting flow of the under gravity. Typically such formulations will include, typically as the oil base of the formulation, a paint stripping solvent. Particularly useful such solvents include non-volatile oil based materials such as benzoate esters, particularly of C 4 and longer alcohols, especially Cg to C-12. particularly branched, alcohols such as 2-ethylhexyl benzoate. The combinations of the invention can provide formulations having practical residence times, particularly on inclined/vertical surfaces that are much longer than non-structured systems and this may enable greater stripper effectiveness and/or more economical use.

Examples

[0090] The following examples illustrate the invention. All parts and percentages are by weight unless otherwise stated. Materials

Synthesis Examples

[0091] Fatty acid oligomer based starting materials

DD1 dimerdiol (2% monomer, 96.5% dimer 1.5% trimer) Pripol 2033 ex Uniqema

[0092] Non-(fattv acid oligomer) diols

D1 1 ,6-hexanediol (MP 39-42⁰C)

D2 ethylene glycol

D3 1 ,4-butanediol

[0093] Isocvanates

IC1 hexamethylene diisocyanate (HDI), Desmodur H ex Bayer

[0094] Catalysts

Cat1 stannous octoate, Tegocat 129 ex Goldschmidt

Cat2 dibutyl tin dilaurate, Fascat ex Arkema lnc

[0095] Other reagents

Aid isostearyl alcohol, Priserine 3515 ex Uniqema

TMP trimethylolpropane

FA1 isostearic acid, Priserine 3501 ex Uniqema

FA2 lauric acid FA1 , Prifrac 2922 ex Uniqema

FA3 stearic acid, Prifrac 2979 ex Uniqema

Est1 methyl isostearate, Priserine 3760 ex Uniqema

[0096] Oligomer melting temperature was measured using differential scanning calorimetry on a Mettler Toledo DSC822-LT machine with STARe software. The samples used weighed about 6 mg and the white transparent crystals were placed in a 40 μl aluminium crucible with pierced lid. Measurements were made using the following thermal profile: the sample was initially held at -15O⁰C for 10 minutes; at -15O⁰C; followed by heating to 200⁰C at 2O⁰CmJn^''' using a nitrogen purge (30 ml.min"¹)

Synthesis Example SE1 :

[0097] This Example illustrates the preparation of an ester-terminated oligourethane stabiliser (OS1). DD1 (346.2 g; 0.638 mol), D1 (27.1 g; 0.229 mol) and FA1 (106.5 g; 0.366 mol) were charged to a 11 flanged flask ("reactor") equipped with an external electrical heater, nitrogen inlet, thermometer, condenser and receiving vessel, central stirrer and addition port. The reactor headspace was sparged with nitrogen. The mixture was heated to 18O⁰C as rapidly as possible (to reduce colour formation and to strip the water from the reaction mixture) with Cat1 (0.38 g; 0.8 g.kg(reaction mix)^"1) added when the temperature reached 14O⁰C. When the temperature reached 18O⁰C the nitrogen flow was stopped and vacuum was applied, at a level below that at which uncontrolled foaming occurred (typically reducing the pressure to ca 20 mbar (absolute) over a period of about 1 hour). These conditions were maintained until the acid value fell to below 0.1 mg.KOH.g-1. (Typically about 6 hours on the laboratory scale.) The mixture was allowed to cool to 6O⁰C and nitrogen admitted to raise the pressure to ambient. On completion of the esterification reaction, IC1 (100.5 g; 1.125 mol) was added through the addition port using a dosing pump at a rate of 150 g.hour¹.kg^''' . During addition the exothermic reaction between diols and diisocyanate raised the temperature, with the addition rate controlled to limit the rate to 50°C.hour-1 , reaching a peak temperature of about 14O⁰C at the end of the addition. This temperature was held until the hydroxyl value fell to 10 mg(KOH).g-¹ (or less). The reaction mixture was discharged and allowed to cool to ambient temperature to yield the oligomer as a slightly yellow hazy waxy solid.

Example SE2:

[0098] DD1 (534.6 g; 0.985 mol), D1 (37.1 g; 0.315 mol), TMP (4.2 g; 0.0315 mol) and

Est1 (260.1 g; 0.854 mol) were charged to the reactor, catalyst Cat1 (0.67 g ; 0.8 g.kg(reaction mix)^"'') added, IC1 (163.9 g; 0.976 mol) dosed and the reaction mix was heated to ca 6O⁰C. IC1 (163.9 g; 0.976 mol) was dosed at 150 g.hour¹.kg^"1 at atmospheric pressure under nitrogen sparge and moderate mixing (150-200 rpm). Once isocyanate dosing was started, the temperature was increased at 5O⁰C. hour¹ to 18O⁰C. When the temperature reached 14O⁰C the nitrogen flow was stopped and vacuum was applied, to promote distillation of the methanol by-product, reducing the pressure to ca 20 mbar (absolute) over a period of about 1 hour). On completion of the reaction the mixture was allowed to cool down and discharged, yielding a slightly yellow hazy solid product.

Example SE3:

[0099] Hydroxylic reagents DD1 (666.1 g; 1.22 mol), D2 (34.5 g; 0.555 mol) and Aid

(132 g; 0.49 mol) were charged to the reactor and heated to 6O⁰C, Cat2 (605 μl; 500 μl.kg^"1) was added and IC1 (373.8 g; 2.22 mol) was added as described in Synthesis Example SE1 with the reaction mix worked up as described in SE1. The reaction mixture was discharged and allowed to cool to ambient temperature to yield the oligomer as a slightly yellow hazy waxy solid.

Example SE4:

[0100] DD1 (377.9 g; 0.696 mol), FA2 (66.8 g; 0.334 mol) and FA3 (92.6 g; 0.326 mol) were charged to the reactor catalyst Cat1 (0.43 g; 0.8 g.kg^'1) added and esterification carried out at 180⁰C as described in Synthesis Example SE1. The mixture was cooled to 60⁰C and D3 (30 g; 0.334 mol) charged, IC1 (30 g; 0.179 mol) dosed and the reaction mix worked up as described in SE1. Example SE5:

[0101] The product was made as described in Synthesis Example SE3, but using DD1

(512.8 g; 0.95 mol), D1 (37.1 g; 0314 mol), Aid (186.3 g; 0.69 mol) and Cat2 (500 μl;

500 μl.kg^"1), then dosing IC1 (263.8 g; 1.57mol) followed by working up.

Example SE6

[0102] The product was made as described in Synthesis Example SE3, but using DD1

(445.6 g; 0.82 mol), D3 (36.8 g; 0.985 mol), Cat2 (500 μl; 500 μl.kg^'1) and Aid (242.8 g; 0.9 mol), then dosing IC1 (275 g; 1.64 mol) followed by working up.

Example SE7

[0103] The product was made as described in Synthesis Example SE3, but using DD1

(440.4 g; 0.81 1 mol), D1 (47.8 g; 0.5 mol), Cat2 (550 μl; 500 μl.kg^"1) and Aid (340 g;

0.885 mol), then dosing IC1 (271.8 g; 1.62 mol) followed by working up.

[0104] The cooled oligomer products may be ground e.g. in a cryogenic centrifugal mill, to produce a powder form for ease of handling and subsequent incorporation into formulations.

[0105] The materials and molar proportions used in the Synthesis Examples are set out in Table SE1 below.

Table SE1

[0106] Materials used in Evaluation Examples

Oligomers

Olig1 PU oligomer of SE1

Olig2 PU oligomer of SE2

Olig3 PU oligomer of SE3

Olig4 PU oligomer of SE4

Olig5 PU oligomer of SE5

Oligβ PU oligomer of SE6

Olig7 PU oligomer of SE7

Oils OiM methyl oleate ester oil - Priolube 1400 ex Uniqema Oil2 isoparafinic oil - Maxpar HWD 37/ 2 ex Cullinet and Associated Ltd Oil3 alkylbenzene oil Solvesso Aromatic 200ND ex ExxonMobil Oil4 paraffinic oil - Ag Oil 7N ex Sunoco Oil5 alkylbenzene oil - Solvesso 200 ex-ExxonMobil Oil6 2-ethyl hexanoate - Prifer 6813 ex Croda

Additives

Carboxylic acids

A2 Acetic

A3 Propionic

A4 Butyric

A5 Pentanoic

A6 Hexanoic

A7 Heptanoic

A8 Octanoic

A2EH 2-Ethylhexanoic

A9 Nonanoic

Ai9 lsononoic

A10 Decanoic

A12 Dodecanoic

A14 Myristic

A16 Palmitic

A2HdD 2-Hexyldecanoic

A18 Stearic

Ai18 lsostearic

A18:1 Oleic

A18:1 ;OH Ricinoleic A18:2 Linoleic

ABz Benzoic

Alkyl amines

Am6 Hexylamine

Am12/14 Primene 81 R (C12-C14 t-alkyl amine mixture)

Carboxylic acid amides

Ad18:1 Oleamide

Ad6 Hexanoamide

M 150CW Monamid 150 CW

MCMA Monamid CMA

M150IS Monamid 150 IS

TMU tetramethyl urea

Miscellaneous

Tw20 Tween-40

Cx300 Carbowax 300

2-PE 2-Phenoxyethanol

Evaluation Method

[0107] Materials were screened for their ability to depress the melting point of polyurethane oligomeric structuring agents (usually simply termed "oligomers"). To facilitate making a uniform melt each oligomer was cryogenically milled using dry ice in a blender. The materials were co-melted with the selected oligomer powder on a hot plate stage. The co-melted products ranged from viscous oils to plastic-like materials. The co-melted products were mixed with the target oil at ambient temperature; where the co-melt is an oil or a soft paste it was shaken in the oil by hand, more solid-like forms of co-melt were sheared into the oil using a high shear mixer. The form of the gel that resulted and the time to achieve gelation (typically from 15 minutes to overnight) were recorded.

Evaluation Example EE1

[0108] Various carboxylic acids were tested for their utility in formulating the oligomer of

SE1 in OiH by the method described above. The acids used, their concentration (in millimoles of acid per gram of oligomer [mol. kg^{' '}'(oligomer)], the concentration of oligomer in the oil (wt% oligomer on oil) are given in Table Eval 1 below. Table Eval 1

(1 ) viscous liquid formed including some gel particles (2) some acid precipitated from the oil Evaluation Example EE2

[0109] Further tests were run as described in EE1 , but using oligomer Olig2 and OiH .

The formulations and results are summarised in Table Eval 2 below.

Table Eval 2

Evaluation Example EE3

[0110] Further tests were run as described in EE1 , but using oligomer Olig3 and OiH .

The formulations and results are summarised in Table Eval 3 below.

Table Eval 3

(1 )the oligomer acid co-melt is a plastic material that was not possible to disperse in the oil

Evaluation Example EE4

[0111] Further tests were run as described in EE1 , but using oligomer Oligi and OiH .

The formulations and results are summarised in Table Eval 4 below. Table Eval 4

Evaluation Example EE5

[0112] Further tests were run as described in EE 1 , but using oligomer Olig5 and OiM .

The formulations and results are summarised in Table Eval 5 below.

Table Eval 5

Evaluation Example EE6

[0113] Further tests were run as described in EE1 , but using various oligomers and Oils.

The formulations and results are summarised in Table Eval 6 below.

Table Eval 6

Evaluation Example EE7

[0114] Further tests were run as described in EE 1 , but using various oligomers and OiH .

The formulations and results are summarised in Table Eval 7 below.

Table Eval 7

Evaluation Example EE8

[0115] Further tests were run generally as described in EE1 , but using non carboxylic acid additives with oligomer Olig1 and OiH . The formulations and results are summarised in Table Eval 8 below.

Table Eval 8

Evaluation Example EE9

[0116] This Example illustrates the use of urea derivatives, particularly tetramethyl urea as a hydrogen bond disruptor with an oligomer oil structurant having a relatively high melting/softening temperature.

[0117] TMU (75 g) was heated in a beaker with structurant Oligδ (25 g) on a hotplate to 13O⁰C for 1 hour and the mixture was stirred using an overhead stirrer. The resulting 25% oligomer solution in tetramethyl urea was then cooled to ambient temperature yielding a colourless clear gel. The ability of this solution to structure oil formulations was tested by reheating the mixture to 5O⁰C in an oven; at this temperature, after minimal initial agitation, a flowable, easily handleable liquid was obtained. This oligomer structurant solution was then added slowly with high shear mixing at room temperature into Oil5 to give a formulation containing 1% by weight of the structurant oligomer. The formulation formed a stable gel which was readily shear thinning. This combination of structurant, hydrogen bond disruptor and oil was used in further testing including an agrochemical active material in AE1 and AE2 below.

Application Examples

[0118] Materials used in Application Examples

Surfactants

Surfi blend of castor oil ethoxylate (Etocas T series) and calcium alkylaryl sulphonate (Atlox 4838B) ex Croda

Surf2 poly(hydroxy stearic acid) non-aqueous dispersant (Atlox LP1 ex Croda)

Surf3 calcium alkylaryl sulphonate (Atlox 4838B ex Croda)

Surf4 alkyd type copolyester polymeric surfactant (Atlox 4914 ex Croda)

Surfδ ca C13 fatty alcohol 20-ethoxylate - (Synperonic A20 ex Croda)

Surfδ polyoxyethylene/polyoxypropylene block copolymer surfactant (Atlas

G-5000 ex Croda)

Oligomer hydrogen bond distruptor combinations

Combi 1 :3 gel mix of Oligθ and TMU from Evaluation Example 9

Comb2 1 :1.24 gel mix of Oligi and A8

Comb3 1 :1 gel mix of Olig 1 and A6

Agrochemical actives

Ag1 lmidacloprid

Ag2 Carbaryl Application Example AE1

An agrochemical formulation was made up as follows:

Material Amount (wt%)

Surfl 10

Ag1 10

Surf 2 0.5

Combi 4

Oil5 78.5

[0119] The formulation was made by dispersing the lmidacloprid and the surfactants in the Oil and then adding the structured oligomer (separately warmed to 5O⁰C), to give a stable gel which was readily shear thinning. The gel formulation was stored for two weeks storage at 54⁰C after which there was only a small (<5%) supernatant oil layer indicating only very limited sedimentation of agrochemical active.

Application Example AE2

[0120] An agrochemical formulation was made up as described in AE 1 but using OiH for the Oil5 in Application Example AE1. After mixing, the formulation formed a stable gel which was readily shear thinning. Storage testing as in AE1 showed only a small (<5%) supernatant oil layer indicating only very limited sedimentation of agrochemical active.

Application Example AE3

[0121] An agrochemical formulation was made up as described in Application Example

AE2, using the blend Comb2 gel (Olig1+A8 at 1.24:1 by weight) and other materials as follows:

Material Amount (wt%)

Surf3 4.09

Surf4 0.63

Surfδ 2.04

Surf6 0.82

Ag2 20

Comb2 4.5

OiH 67.92

Stability testing showed no separation after one month storage at ambient temperature. Application Example AE4

[0122] An agrochemical formulation was made up as described in AE1 but using 4 wt% of the blend Comb2 gel (Olig1+A6 at 1 :1 by weight) and adjusting the amount of OiH to

68.42. Stability testing showed no separation after one month storage at ambient temperature.

Application Example AE5

[0123] A gelled oil based formulation was made up by mixing Comb3 (a preformed gel of Oligi and A6 at 1 :1 by weight) into Oil6 at a concentration of 4% (2% active oligomer) by weight, to give a gel at ambient temperature in about 1 hour. This gel was brushed onto a vertical film of acrylic paint on a glass slide (drawn with a 1.5Dm doctor blade and dried for 24 hours at ambient temperature). Three minutes after application of the gel, a paper towel was rubbed over the acrylic paint film 15 times and the paint film was completely removed. A control experiment using a paper towel 15 cycles over the untreated paint film gave no paint removal. It was noted that the structurant oligomer acted to increase the residence time of the stripping solvent on the vertical surfaces by inhibiting flow under gravity.

Claims

What is claimed is:

1. A combination of an oligomer oil structurant which includes urethane and/or urea linkages and residues of a dimer and/or trimer component; and a hydrogen bond disruptor.

2. A combination as claimed in claim 1 wherein the hydrogen bond disruptor is present in a proportion of from 0.5 to 20 mol hydrogen bond disruptor per kg of oligomer oil structurant.

3. A combination as claimed in either claim 1 or claim 2 wherein the oligomeric structurant includes a dimer component unit of the formula (I):

-(X)-(D)-(X)CO-NH-R¹- (I) where

-(D)- is a difunctional residue which is or includes fatty acid dimer residues; each X is independently -O- or -NH-; and

R¹ is a C-| to Cβo hydrocarbylene group; and/or a trimer component unit of the formula (III):

-(X')₂-(T)-(X')CO-NH-R¹⁰- (III) where

-(T)- is a trifunctional residue which is or includes fatty acid trimer residues; each X' is independently -O- or -NH-; and

R¹^ is a C 1 to Cøo hydrocarbylene group.

4. A combination as claimed in any one of claims 1 to 3 wherein the oligomeric structurant includes repeat units of the formula (Ia):

-(X)-(D)-(X)C(O)NH-R¹-NHC(O)- (Ia) urethane repeat units of the formula (Ib)

-0-(D)-OC(O)NH-R¹ -NHC(O)- (Ib) and/or urea repeat units of the formula (Ic):

-NH-(D)-NHC(O)NH-R¹ -NHC(O)- (Ic) where D, R¹ and each (X) are independently as defined for formula (I) in claim 2.

5. A combination as claimed in any one of claims 1 to 4 wherein the oligomeric structurant is of the formula (II):

R²-[(X)-(DHX)OCNH-R¹-NHCO]_m-(XHD)-(X)-R² (II) where

R¹ , (X) and -(D)- are independently as defined for formula (I); each R² is independently H₁ a group -C(O)R^, where R^ is a hydrocarbyl group, particularly a C-_| to CQQ, more usually a Ci to C44, especially alkyl, group, or a group -C(O)NH-R¹ -NHC(O)-(X)-R*; or a group -C(O)NH-R⁴; or the group -(X)R² is a group -0(A0)_n-(C0)pR⁴, where each OA is independently an ethyleneoxy or propyleneoxy group, n is from 1 to 50, p is O or 1 ; where each R1 and X are independently as defined above, each R⁴ is independently a hydrocarbyl group, particularly a C-| to CQQ, more usually a

C-_| to C44, especially alkyl, group; and m is from 1 to 25.

6. A combination as claimed in any one of claims 1 to 5 wherein the oligomeric structurant includes residues of a trifunctional chain extender, particularly trimer acid or a trimer based hydroxyl or amino functional reagent, and/or residues of a non-dimer diol or diamine.

7. A combination as claimed in any one of claims 1 to 6 wherein the hydrogen bond disruptor is one or more, particularly CQ to C^. carboxylic acid; medium to long chain, particularly CQ to C20. alkyl amine; carboxylic acid, particularly Cs to C20 fatty ^acid, amide; dicarboxylic acid, particularly carbonic acid, diamide, particularly alkyl urea, or ether, particularly (poly)ethers, especially long chain polyethylene glycols or fatty, particularly CQ to

C20. alcohol, or polyalkoxylates, particularly ethoxylates as for example 3 to 50, especially 5 to 30 ethoxylates, or polyalkoxylates, particularly ethoxylates as for example 3 to 50, especially 5 to 30 ethoxylates, of fatty acid partial esters of polyols such as glycerol, sorbitol or sorbitan, or mixture of two or more of these.

8. A combination as claimed in claim 7 wherein the hydrogen bond disruptor is a C-₎ to C22_> particularly a C4 to C-|8. especially a CQ to C-|2_> fatty acid, or a C3 to C-|β, particularly a CQ to Ci 2. especially a CQ to C-I Q. alkyl amine.

9. A combination as claimed in claim 7 wherein the hydrogen bond disruptor is a tetra-(C-) to Cs alkyl)urea, particularly tetramethyl-, tetraethyl- or tetrabutyl-urea.

10. A combination as claimed in any one of claims 7 to 9 wherein the amount of the hydrogen bond disruptor incorporated with the structurant oligomer is from 10 to 80%, particularly 30 to 60%, especially 40 to 50%, by weight of the oligomer.

11. A method of making a combination as claimed in any one of claims 1 to 10 which comprises mixing the oligomeric structurant and the hydrogen bond disruptor at a temperature near, particularly above the melting temperature of the oligomeric structurant, particularly at such a temperature in the range 70 to 18O⁰C, especially 100 to 160⁰C.

12. A structured oil formulation which comprises a combination as claimed in 1 to 10 dispersed or dissolved in an oil.

13. A formulation as claimed in claim 12 wherein the oil is one or more: alcohols, liquid polyols, fatty alcohol polyalkoxylates, ester oils, natural triglycerides, methylated natural triglycerides; aromatic ester oils; branched liquid fatty alcohols; branched liquid fatty acids; hydrocarbons; or a mixture of two or more such types of oil.

14. A formulation as claimed in either claim 12 or claim 13 wherein the concentration of the oligomeric structurant is from 0.2 to 15% by weight of the formulation.

15. An agrochemical concentrate which comprises a structured formulation as claimed in any one of claims 12 to 14 and further including an agrochemically active component.

16. A concentrate as claimed in claim 15 wherein the agrochemically active component is one or more: plant growth regulator, herbicide, and/or pesticide, particularly one or more: sulfonyl urea herbicides, triazine herbicides, thiocarbamate fungicides, benzenedicarbonitrile fungicides, dicarboximide fungicides, halogenated phthalonitrile fungicides, benzimidazole fungicides, azole fungicides, carbamate insecticides, phenyl organothiophosphate insecticides, cyclodiene insecticides, or a mixture of two or more such types of agrochemically active component.

17. A concentrate as claimed in claim 16 wherein the concentration of the agrochemically active component is from 0.5 to 30% by weight of the formulation.

18. A concentrate as claimed in any one of claims 15 to 17 which additionally contains one or more surfactants, solvents, dispersants, electrolytes and/or wetters, particularly where the concentration of surfactant is from 5 to 35 % by weight of the total formulation.

19. A concentrate as claimed in any one of claims 15 to 18 which comprises the following components: a) from 10 to 95 wt% of an oil, b) from 0.1 to 15 wt% of oligomeric structurant, c) from 0.5 to 30 wt% of agrochemically active component, d) optionally from 5 to 35 wt% of surfactant, e) optionally from 0.1 to 45 wt% of solvent.

20. A spray formulation which comprises a concentrate as claimed in any one of claims 15 to 19, diluted with water.

21. A method of making up a spray formulation which comprises diluting a concentrate as claimed in any one of claims 15 to 19 with water.

22. A method of treating vegetation which comprises spraying in which the vegetation or the ground adjacent to vegetation with a spray formulation as claimed in claim 20 or made by the method of claim 21.